Embodiment
At first, epoxy acrylate of the present invention is described.
Epoxy acrylate of the present invention is represented by above-mentioned general formula (1).At this, X representes Wasserstoffatoms or methyl.Z representes the alkyl of C1~C6, all can be the same or different.A representes 0~4 integer.
Epoxy acrylate by above-mentioned general formula (1) expression can carry out acroleic acid esterification and make through making by the diepoxy phenyl compound and unsaturated carboxylic acid (being vinylformic acid, methylacrylic acid or the implication that the comprises both) reaction of above-mentioned general formula (5) expression.Therefore, the kind of Z is from the structure of the diepoxy phenyl compound that uses as raw material.Consider that from the aspect of the characteristic of the easy property of the acquisition of diepoxy phenyl compound, the epoxy acrylate that obtains preferred Z is the alkyl of C1~C6, a is 0~4 integer, and preferred especially a is 0~1 integer.
By the diepoxy phenyl compound of above-mentioned general formula (5) expression, have except that Z on the benzene skeleton, to have replaced the structure of 2 epoxy ethyls, as isomer, have 1,2-two replaces bodies (ortho position body), 1,3-two replaces bodies (contraposition body) and 1,4-two replacement bodies (contraposition body).As the diepoxy phenyl compound that uses among the present invention; Can be these mixture of isomers; But consider from both viewpoint that has thermotolerance and LV property concurrently; The containing ratio of position body and contraposition body is high between preferred, can preferably use contain that 90 weight % are above, preferred 95 weight % are above between the material of position body and contraposition body.
Epoxy acrylate of the present invention can be made through diepoxy phenyl compound and unsaturated carboxylic acid are reacted.In this reaction, the epoxy ring-opening of diepoxy phenyl compound and produce ester bond with unsaturated carboxylic acid and carry out bonding.This open loop can be in any generation of α position and β position, in the open loop of α position the epoxy acrylate (α affixture) of above-mentioned general formula (1) become staple, in the open loop of β position the epoxy acrylate (β affixture) of above-mentioned general formula (2) become minor component.There are two kinds in the epoxy acrylate of general formula (2).That is the A in the general formula (2),
1And A
2Both for by the situation that contains ester bond group (β affixture) of formula (3) expression and the A in the general formula (2)
1For containing ester bond group (β affixture), A by formula (3) expression
2Be two kinds by the situation that contains ester bond group (α affixture) of formula (4) expression.The former is called full β affixture, the latter is called half β affixture, both are gathered be called the β affixture.The generation ratio of full β affixture is compared enough low with the generation ratio of half β affixture.Need to prove the A in the general formula (2)
1And A
2Both for identical with general formula (1) by the situation that contains ester bond group (α affixture) of formula (3) expression.
In above-mentioned method of manufacture, the generation ratio of α affixture and β affixture is 100/0.01~100/70 with molar ratio computing usually, is preferably 100/0.1~100/50.Therefore, in above-mentioned method of manufacture, can obtain epoxy acrylic ester composition of the present invention usually.The epoxy acrylate of general formula (1) can separate from above-mentioned resultant of reaction or epoxy acrylic ester composition through known method.Epoxy acrylic ester composition of the present invention with the epoxy acrylate of general formula (1) as staple.At this, as staple, be meant contain total epoxy acrylate 60 moles more than the %, as minor component, be meant and contain 40 moles below the %.
Epoxy acrylate of the present invention or epoxy acrylic ester composition, can through with diepoxy phenyl compound and unsaturated carboxylic acid as required in the presence of catalyzer, stopper, 50~200 ℃ down reaction made in 1~50 hour.
The reaction ratio of diepoxy phenyl compound and unsaturated carboxylic acid is preferably 100/5~5/100 with the molar ratio computing of diepoxy phenyl compound and unsaturated carboxylic acid, more preferably 100/10~10/100 reaction ratio.
As spendable catalyzer this moment, can enumerate the microcosmic salt etc. of the phosphine class, tetra-n-butyl tetraphenyl boric acid phosphorus etc. of the quaternary ammonium salt, imidazolium compounds, triphenylphosphine etc. of the tertiary amine, tetramethyl ammonium chloride etc. of the alkali metal hydroxide, triethylamine, benzyldimethylamine etc. of for example sodium hydroxide, Pottasium Hydroxide etc.These catalyzer can use separately also can be also with two or more.As the catalyzer usage quantity, according to the catalyzer that uses and difference with respect to 100 moles of diepoxy phenyl compounds, is preferably 0.01~100 mole, further be preferably 0.1~80 mole.
Spendable stopper when reacting; Can be for as the known stopper of the stopper of vinyl compound; Can enumerate the phenols etc. of the amine, phenol, methoxyphenol, quinhydrones, tert-butyl catechol, butylhydroxy toluene, cresols etc. of for example phenothiazine, methoxyl group phenothiazine, hindered amine etc., be preferably phenols.These stoppers can use separately also can be also with two or more.As the stopper usage quantity, according to the catalyzer that uses and difference with respect to 100 moles of diepoxy phenyl compounds, is preferably 0.001~10 mole, further be preferably 0.01~1 mole.
When reacting, also can be as required with an organic solvent.As organic solvent, can enumerate the ketone series solvent etc. of the aromatic hydrocarbons series solvent, MIBK, MEK etc. of for example toluene, YLENE etc.As the usage quantity of solvent, total weight 100 weight parts with respect to diepoxy phenyl compound and unsaturated carboxylic acid are generally 50~5000 weight parts, are preferably 100~2000 weight parts.
When reacting, also can import air or oxygen as required.Consider from the aspect of the control of reaction, preferably import air and get final product.
The diepoxy phenyl compound, can use through superoxide to divinyl benzene compound epoxidation material.Owing to do not use epoxy chloropropane, the cl content of the compound that therefore obtains is few.As superoxide, can use the peracid, hydrogen peroxide or the organo-peroxide that obtain through usual method.
As the polymerization starter that in acrylic resin composition of the present invention, uses; Can be for as the known polymerization starter of the polymerization starter of vinyl compound, the irradiation or the radical polymerization initiator of the active energy ray through using ultraviolet ray, electron beam etc. are cured.
When the curing that utilizes uviolizing, in solidification compound, add Photoepolymerizationinitiater initiater in advance.
As Photoepolymerizationinitiater initiater; Not special the qualification; Can enumerate through the be excited common Photoepolymerizationinitiater initiater of the type that produces radical of ultraviolet irradiation; Particularly; As suitable initiator; But the bitter almond oil camphor class of illustration bitter almond oil camphor, benzoin methylether, ethoxybenzoin, benzoin iso-propylether, Alpha-Methyl bitter almond oil camphor etc., Alpha-hydroxy isobutyl-benzophenone, UVNUL MS-40, to the methyldiphenyl ketone, to chlorobenzophenone, to benzophenone, the methyl phenyl ketone, 9 of diethylamino UVNUL MS-40 etc., the sulfocompound class of the anthraquinone class of 10-anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone etc., phenylbenzene disulfide, tetramethyl-thiuram disulfide etc. etc.
These Photoepolymerizationinitiater initiaters can separately or mix two or more uses, and as its use level, recommending the total amount with respect to polymerizable compound is about 0.1~10 weight %.
In addition, in order to promote to utilize the photopolymerization reaction of Photoepolymerizationinitiater initiater, also can add sensitizer.
This sensitizer is not special to be limited; Particularly; But the thioether class of the alkylphosphines class of the tertiary amines of illustration triethylamine, trolamine etc., triphenylphosphine etc., thiodiglycol etc. etc., as its use level, recommending the total amount with respect to polymerizable compound is about 0.01~5 weight %.
As ultraviolet light source, can use chemical lamp, Cooper-Hewitt lamp, high pressure mercury vapour lamp, xenon lamp, metal halide lamp etc.
Under situation about being cured through electron beam, need not use Photoepolymerizationinitiater initiater, sensitizer, the electron beam that shines the irradiation dose about 1~20Mrad through electron beam generating device commonly used, usually gets final product.
The fashionable employed radical polymerization initiator of radical polymerization is not special to be limited in that the acrylic resin composition that the present invention relates to is carried out; Particularly; But the azo cpd of the superoxide of illustration Lucidol, peroxo-carbonic acid diisopropyl ester, lauroyl peroxide etc., Diisopropyl azodicarboxylate etc., these polymerization starters can use separately also can be also with two or more.What polymerization starter preferably used separately according to purposes that thermofixation uses uses with photocuring.
The usage quantity of these polymerization starters, according to the stopper that uses and difference, preferably the total amount with respect to polymerizable compound is 0.001~5 weight part, further is preferably 0.01~1 weight part.Wherein, this ratio of mixture changes according to the kind generation the earth of the solidifying agent that uses, and therefore needs the suitable top condition of confirming.
In acrylic resin composition of the present invention, can add the polymerizable monomer that utilizes heat or light as required.Utilize the polymerizable monomer of heat or light as these, can be the polymerizable monomer of known utilization heat or light, below illustrative various propenoate based compounds can separately or mix two or morely, also can be used as the solidified nature composition and use.
As simple function property (methyl) propenoate; But illustration (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) Bing Xisuandingzhi, (methyl) NSC 20949, the just own ester of (methyl) vinylformic acid, (methyl) propylene 2-ethylhexyl, (methyl) decyl acrylate, (methyl) lauryl acrylate, (methyl) stearyl acrylate base ester, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, dimethyl aminoethyl (methyl) propenoate, diethylamino ethyl (methyl) propenoate, 3-chloro-2-hydroxypropyl (methyl) propenoate, 2,3-dibromopropyl (methyl) propenoate etc.
As two functionalities (methyl) propenoate; But illustration ethylene glycol bisthioglycolate (methyl) propenoate, Diethylene Glycol two (methyl) propenoate, triethylene glycol two (methyl) propenoate, TEG two (methyl) propenoate, polyoxyethylene glycol two (methyl) propenoate, Ucar 35 two (methyl) propenoate, dipropylene glycol two (methyl) propenoate, tripropylene glycol two (methyl) propenoate, W 166 two (methyl) propenoate, propane diol two (methyl) propenoate, glycerine two (methyl) propenoate, 1; 3-butyleneglycol two (methyl) propenoate, 1; 4-butanediol two (methyl) propenoate, 1; 5-pentane diol two (methyl) propenoate, 1; Two (methyl) propenoate of the alkylene oxide affixture of the diacrylate of the acetal of 6-hexane diol two (methyl) propenoate, NSC 6366 two (methyl) propenoate, two (oxygen methyl) three ring [5.2.2.02,5] decane two (methyl) propenoate, cyclohexane diol two (methyl) propenoate, two [(methyl) acryloyl-oxy ylmethyl] hexanaphthene, TriMethylolPropane(TMP) and pivalyl aldehyde, hydroxypivalic acid DOPCP diacrylate, dihydroxyphenyl propane-two (methyl) propenoate, dihydroxyphenyl propane etc.
As three and even four functionality (methyl) propenoate, but illustration trimethylolpropane tris (methyl) propenoate, tetramethylolmethane four (methyl) propenoate, Dipentaerythritol five (methyl) propenoate, Dipentaerythritol six (methyl) propenoate etc.
As the acrylic polymerizable oligopolymer, but (methyl) propenoate of (methyl) propenoate of illustration epoxy (methyl) propenoate, carbamate (methyl) propenoate, polyester (methyl) propenoate, polyhutadiene oligopolymer, polyamide based (methyl) acrylic acid oligomer, trimeric cyanamide (methyl) propenoate, cyclopentadiene oligopolymer, (methyl) propenoate of organosilicon oligopolymer etc.
In addition; Except that above-mentioned acrylic ester solidified nature composition; Can suit and with other polymerizable monomer, for example terminal olefin of the vinyl based compound of vinylbenzene, vinyl acetate, vinylchlorid, vinylidene chloride, vinyl cyanide, vinyl ether, propenal etc., ethene, divinyl etc. etc.These utilize the polymerizable monomer of heat or light to use separately also can be also with two or more.Utilize the polymerizable monomer of heat or light preferably separately to use thermopolymerization property monomer and photopolymerization monomer according to purposes.
In acrylic resin composition of the present invention, also other composition of weighting agent, fiber, coupling agent, fire retardant, releasing agent, whipping agent etc. as required.Weighting agent as this moment; Can enumerate for example polyethylene powders, polypropylene powder, quartz, silicon-dioxide, silicate, lime carbonate, magnesiumcarbonate, gypsum, wilkinite, fluorite, titanium oxide, carbon black, graphite, red stone, aluminium powder form, iron powder, talcum, mica, kaolin etc.; As fiber, can enumerate for example cellulosic fibre, spun glass, thomel, aramid fiber etc.As coupling agent, can enumerate for example silane coupling agent, titanate coupling agent etc.As fire retardant, can enumerate for example brominated bisphenol A, ANTIMONY TRIOXIDE SB 203 99.8 PCT, phosphorus series compound etc.As releasing agent, can enumerate for example stearate, organosilicon, wax etc.As whipping agent, can enumerate freonll-11 for example, ethylene dichloride, butane, pentane, dinitropentamethylenetetramine, p-toluene sulfonyl hydrazide, or freonll-11, ethylene dichloride, butane, pentane etc. are filled in swelling property thermoplastic resin particle in the shell of polyvinyl vinylidene chloride, vinylbenzene-(methyl) Yodo Sol GH 28 etc.
Acrylic resin composition of the present invention can be with easily processing the acrylics cured article with the same method of known method in the past.For example with the polymerizable monomer of epoxy acrylate of the present invention or epoxy acrylic ester composition, polymerization starter, the utilization heat of adding as required or light and other additive, use forcing machine, kneader, roller etc. to be fully mixed to reach and evenly obtain acrylic resin composition as required; This acrylic resin composition used after fusion casting mold or shift forming mill etc. form; Reheat to 80~200 ℃ can obtain cured article thus.
In addition; Also can obtain cured article as follows: make acrylic resin composition of the present invention be dissolved in solvent; Make it contain the base material that is dipped in spun glass, thomel, trevira, tynex, sapphire whisker, paper etc.; Carry out heat drying, the prepreg that obtains is carried out hot compacting.For example with epoxy acrylate of the present invention or epoxy acrylic ester composition, polymerization starter and other heating such as additive, be stirred to and reach even; It is contained be dipped in woven fiber glass; Heat partial desiccation and remove solvent composition and obtain prepreg; Overlappingly need this prepreg of number and more than 1 hour, can make the glass fabric layer lamination thus 80~200 ℃ of following heating and pressurizing.
As the concrete example of spendable dilution this moment with solvent; Preferred toluene, YLENE, methyl ethyl ketone, MIBK, methylcyclohexane etc.; Its usage quantity; Using the total weight of solvent with respect to acrylic resin composition with this dilution is 10~70 weight %, is preferably 15~65 weight %.
The cured article that obtains like this has high heat resistance, toughness, chemical-resistant and hardness, and therefore acrylics cured article of the present invention can use in extensive fields such as optical resin.The protective membrane of colour filter of particularly, also can be preferably coating material solidified with resin or electroless plating resist, glass substitute material and liquid crystal etc. with resin, hard coat material, UV as solder resist.Particularly excellent as the optical material of lens, prism, colour filter or these protective membrane etc.
Embodiment
Below for further clear and definite characteristic of the present invention, enumerate embodiment and describe particularly.Need to prove that " part ", " % " in the literary composition all represent weight basis.
Embodiment 1
In the glass there-necked flask of the 300ml that prolong, TM, blast tube are installed, put into diepoxy ethylbenzene (position body/contraposition body=7/3) 8.10g (50mmol), vinylformic acid 18.01g (250mmol), benzyltriethylammoinium chloride 0.23g (1mmol), butylated hydroxytoluene 0.055g (0.25mmol), toluene 100ml; While importing air, make its reaction 24 hours 80 ℃ of following heated and stirred.After the reaction, be cooled to room temperature, clean three times with zero(ppm) water 100ml.The separation of methylbenzene layer, heat up in a steamer toluene after, through ETHYLE ACETATE+hexane (4:6) is made with extra care as the silicagel column of developping solution.Obtain the diepoxy propenoate benzene 9.34g (yield 61%) of water white thick liquid.Mensuration diepoxy propenoate benzene
1H-NMR,
13C-NMR spectrum.
13The result that C-NMR measures is the α affixture: β affixture=5:1.Will
13C-NMR spectrum is shown in Fig. 1.
Comparative example 1
In the glass there-necked flask of the 500ml that prolong, TM, blast tube are installed, put into Styrene oxide 98min. 50.00g (416mmol), vinylformic acid 29.98g (416mmol), triphenylphosphine 1.09g (4.16mmol), 4-tert-butyl catechol 0.346g (2.08mmol), toluene 100ml; While importing air, make its reaction 24 hours 60 ℃ of following heated and stirred.After the reaction, be cooled to room temperature, clean three times with zero(ppm) water 100ml.The separation of methylbenzene layer, heat up in a steamer toluene after, through ETHYLE ACETATE+chloroform (2:8) is made with extra care as the silicagel column of developping solution.Obtain the epoxy acrylate benzene 54.37g (yield 68%) of water white liquid.
Comparative example 2
In the glass there-necked flask of the 500ml that prolong, TM are installed, mix quinhydrones 51.0g, epoxy chloropropane 92.0g, sodium hydroxide 40.0g, water 200.0g, under the reflux temperature, make its reaction 14 hours.After the reaction, add chloroform 600ml and extract.Use the dried over sodium sulfate organic layer.Behind the filtration under diminished pressure, remove chloroform, obtain having the epoxy compounds of quinhydrones skeleton with drying under reduced pressure.In the glass there-necked flask of the 500ml that prolong, TM, blast tube are installed, in this epoxy compounds 90.0g, mix vinylformic acid 76.0g, triethyl benzyl ammonia chloride 2.0g 、 diox 200ml, with mechanical stirrer stir and on one side 70 ℃ under make its reaction 6 hour on one side.After the reaction, add entry 600ml and diethyl ether 600ml carries out separatory.Use the dried over sodium sulfate organic layer.After removing sodium sulfate with filtration under diminished pressure, remove diethyl ether Ji behind the diox, through ETHYLE ACETATE+chloroform (2:8) is made with extra care as the silicagel column of developping solution with drying under reduced pressure.Obtain the diepoxy acryliccompound 71.22g (yield 72%) with quinhydrones skeleton of water white thick liquid.
Embodiment 2
To diepoxy propenoate benzene 100 weight parts of embodiment 1, as イ Le ガ キ ュ ア 184 (チ バ ス ペ シ ャ リ テ ィ ー ケ ミ カ Le ズ Co., Ltd. system of polymerization starter; Trade(brand)name) 5 weight parts carry out mixing, the modulation group compound.It is coated on sheet glass and the aluminium dish, cover demoulding PET film, use high pressure mercury vapour lamp to reach 600mJ/cm with the energy exposure amount
2Mode carry out uviolizing, it is solidified, obtain membranaceous cured article.
Comparative example 3
Except that epoxy acrylate benzene 100 weight parts that use comparative example 1, all the other and embodiment 2 be the modulation group compound likewise, obtains membranaceous cured article.
Comparative example 4
Except that diepoxy acryliccompound 100 weight parts that use comparative example 2, all the other and embodiment 2 be the modulation group compound likewise, obtains membranaceous cured article.
The mensuration of the thermal expansivity (α 1) below the pencil hardness of the cured article that obtains, glass transition point and the glass transition point.Its result is shown in table 1.
For pencil hardness, for being cured as, it becomes filming of 10~20 μ m, measure under the 1kg increasing the weight of based on JISK5600, represent with the hardness that forms the hardest pencil of hindering.
For glass transition point, thermal expansivity (α 1);, heat sizing device (TMA/SS) through エ ス ア イ ア イ Na ノ テ Network ノ ロ ジ ー Co., Ltd. and under nitrogen atmosphere, try to achieve as sample with material that the membranaceous cured article that obtains in embodiment 2, comparative example 3 or the comparative example 4 is processed length 20mm, width 5mm, thickness 0.1mm with the condition of 7 ℃/minute of heat-up rates.
[table 1]
As stated, the thermotolerance of novel epoxy acrylic ester cpds of the present invention, low heat expansion property are excellent.
The possibility of the utilization on the industry
Epoxy acrylate of the present invention; Compare with epoxy acrylate in the past; Thermotolerance, low heat expansion property, high refractive index are excellent, can be provided at that solder resist is coating material solidified with resin, hard coat material, UV with resin or electroless plating resist, useful epoxy acrylate, acrylic acid series compsn and cured article in the optical resin of the colour filter of glass substitute material, liquid crystal etc.